Aqueous wool treating baths comprising chloroprene methacrylate copolymers



Patented Aug. 2 4, 1948 AQUEOUS WOOL TREATING nA'rns coM- rmsmo. CHLOROPRENE METHACBYLATE ooronmns John B. Rust, East Hanover, N. 1., assignor to Montclair Research Corporation, a corporation of New Jersey No Drawing. Original application March 26,

1946, Serial No. 657,335. Divided and this application April 17, 1947, Serial No. 742,199

This invention relates to the shrinkproofing of wool, to methods for obtaining shrinkproofed wool, to the products resulting from such treatment, and to materials utilized for those purposes.

Among the objects of the present invention is Other objects include shrinkproofed wool and wool containing fabrics.

Still further objects include treating baths and other materials for conditioning wool for purposes set forth above.

Other and further objects and advantages of the present invention will appear from the more detailed description set forth below, it being understood that this more detailed description is given by way of illustration and explanation only, and not by way of limitation, since various changes therein may be made by those skilled in the art without departing from the scope and spirit of the present invention.

In accordance with th present invention, the wool either as raw wool, yarn, knit, woven goods or mixed goods, is shrinkproofed with a synthetic choloprene polymer or of such polymer together with other polymers, latices, etc., the amount of such added or additional polymers being insufllcient to interfere with the shrinkproofing effect desired. The amount of chloroprene polymer or modified polymer as set forth above utilized on the wool will generally not be less than 1% nor more than 25% based on the weight of the wool.

The best shrinkproofing effects are obtained with the chloroprene polymer alone, chloroprene copolymers with butadiene-1.3,' or mixtures of such chloroprene polymers with other straight butadiene-LB polymers or butadiene-L3 homolog polymers; and such materials may be used alone or in any proportions to give notably superior nonfelting effects than when other polymers, latices, faetice, etc., are present. The butadie'ne-L3 derivatives that may be employed as polymers with the chloroprene polymer include butadiene-l.3 itself, isoprene, dimethyl butadiene, ethyl butadiene, ethoxy andmethoxy-butadiene, cyano butadiene, and the like, in all instances the butadiene-1.3 derivatives giving the best results. It will be seen that both copolymeric materials as well as mixtures of polymers may be employed.

6 Claims. (Cl. 260-29)!) 2 It has been found that certain unexpected advantages and results accrue in using copolymeric materials. For example, while straight polychloroprene gives a very satisfactory shrinkproofin effect, there is present a somewhat harsh feel to the wool, and straight polybutadiene-L3 gives satisfactory shrinkprooflng but tends to give a slight sticky or greasy feel, the copolymers of those stated derivatives such as that of Example 12 hereinafter set forth, gives shrinkproofing with neither harshness nor stickiness.

For some purposes, however, other polymers, latices, and, factices may be employed to modify the effects obtained, such added materials, however, being used in limited proportions and in no event to produce an undesirable effect on the shrinkprooflng of the woolwithin the limits desired. Such materials which may be utilized with the chloroprene polymer or the chloroprene polymer together with other butadiene-1.3 polymers and butadiene-L3 homolog polymers include polymerizable vinyl compounds and other materials such as the alkyl acrylates such as ethyl acrylate, the alkyl methacrylates such as methyl methacrylate, styrene and its derivatives such as a,p dimethyl styrene and dichlorostyrene, an acrylonitrile such as acrylonitrile, methacrylonitrile, etc., vegetable factices, natural rubber latices, etc. Here again, either copolymersmay be prepared or mixtures of polymers utilized. And unexpected results are obtainable with such combinations,

as for example, the chloroprene-acrylonitrile copolymer gives excellent shrinkage control combined with avery good band. Or the alkyl acrylate copolymers with chloroprene may be used to give increased abrasion resistance. For most of these combinations, from the standpoint of obtaining the best results in shrinkproofing, limitations on proportions are given, it being understood, however, that satisfactory results may sometimes be obtained with proportions outside of those stated depending on the particularmaterials present and their manner of utilization. Thus with the acrylates, particularly the alkyl acrylates, they should generally not exceed about of the total polymers present up to about 40% of methyl acrylate, up to about 50% of ethyl acrylate, and up to about 60% of butyl acrylate being indicated. With the methacrylates, particularly the alkyl methacrylates, not over about 50% of the total polymers present should be used, up to about 20% of methyl methacrylate, up to about 50% of ethyl methacrylate, and up to about 40% of butyl methacrylate, being indicated. With styrene and its derivatives there may be up to 60% of the total of polymers present, for example, not more than 60% styrene although up to about 30% gives the best results, and up to about 40% of dimethyl styrene or dichlorostyrene. With acrylonitriles up to about 40% may be used, the effects obtained depending to some extent on the builer present. With substances like isopropenyl methyl ketone and its homologs from 5 to gives the best results while amounts of from to about are usable. With vinyl esters up to about may be used of esters such as vinyl acetate and vinyl chloride. With vegetable oil factices about 40% represents the better upper limit based on the total weight of polymer and factice present, while with natural rubber latices the latter should not exceed about 75% of the total weight of latex and polymer present. of course, various combinations of the copolymers as set forth above may be employed, and where proportions are indicated above for particular materials, similar proportions are best observed in such combinations.

The chloroprene polymer containing composition may be applied to the wool in any desired way. Such compositions may be applied to the wool,. for example, by padding the wool material with aqueous emulsions of such chloroprene polymer compositions utilizing such aqueous emulsions containing an amount of the polymer sufficient to deposit the polymer on the wool in an amount to give the shrinkproofing eiiect. Thus baths containing about 5% of the polymer may be used for pad-ding purposes or the bath may contain from 1 to of the polymer.

Desirably the chloroprene polymer containing materials can be utilized in the form of aqueous emulsions utilized to deposit the polymer on the wool by exhaustion processes. Thus an aqueous bath containing the chloroprene polymer in emulsion form together with emulsifying agents and desirably with conditioning electrolytes may be utilized. Baths used for deposition of the copolymer by exhaustion will generally contain from 1-2 to 20% and preferably about 5% of the copolymer.

'Such baths may be made in substantially stable condition so that no deposition of the polymer occurs under ordinary conditions. However, the addition of sufiicient strong electrolyte may be utilized to cause exhaustion of the bath and deposition of the polymer on the wool fibers. Ex-

haustion of the bath may be made to take place with varying rapidity depending mainly upon temperature and electrolyte concentration.

The amount of electrolytes utilized to cause exhaustion of the bath may vary over substantial limits but suflicient electrolyte should be present to condition the bath so that the bath although stable in the absence of wool fibers, will deposit the polymer in the presence of the conditioning electrolyte. Thus the electrolyte content may vary between from about 25% to about 500% (based on the weight of the chloroprene polymer derivative present. As such electrolyte,

water-soluble salts may be used, desirably such.

salts which do not precipitate the polymer. The following are exemplary: sodium sulfate, sodium chloride, sodium bromide, sodium iodide, sodium phosphate, sodium sulfamate, sodium sulflte, sodium bisulfate, sodium bisulflte, sodium nitrate, sodium acetate, and the like, and similar salts of potassium, lithium, caesium, and so forth. Salts like zinc chloride may also be used where the coagulation is not too serious, any polymer is present in small particulate form, and the particles may be redispersed by stirring. Neutral salts, specifically salts of strong bases and strong acids, particularly inorganic salts. are preferred. The term conditioning electrolyte is used hereinafter to cover such electrolytes which produce the desired deposition of the polymer in the baths by exhaustion methods as set forth above.

The temperatures at which the polymer or bath containing the polymer is applied to the wool may vary from room temperatures to the boiling points of the bath and more desirably there are utilized temperatures above 40? C. Padding operations may take place at ordinary temperatures or at elevated temperatures. The exhaustion bath methods are desirably carried out at temperatures from 40 C. to the boiling point of the bath. The process can be applied before or after fulling, weaving, scouring and the like operations. In some cases it can be applied in the dye bath. Mixed goods including wool-cotton, wool-rayon, etc., can be treated by this method without any deleterious effect. The wool may be subjected to a pretreatment, as for example. treatments with acids such as acetic acid, or chlorination or bromination, before being treated in accordance with the present invention. The acetic acid pretreatment of the wool is particularly desirable.

When emulsions containing the chloroprene polymer are employed, emulsifying agent may be any anionic emulsifying agent stable under the conditions of the bath at the temperatures employed. Baths having a pH above 7 may desirably .be employed where the material is to be stored or kept for some length of time since reater stability of bath may be produced in this way. However, for deposition purposes a bath having a pH below 7 is desirabl utilized but the invention is not limited to the use of that pH concentration. Emulslfying agents which may be used include sodium lauryl sulfonate, sodium alkyl naphthalene sulfonates, long chain alkyl sodium sulfonates, sodium dioctyl suli'osuccinate, etc. There may also be used neutral non-cationic emulsifying agents such as mannitol monolaurate, the reaction product of protein degradation products with acid chlorides, ethylene oxide reaction products with fatty acid, fatty alcohols, and the like.

After treatment of the wool in accordance with the present invention it is desirably rinsed and dried. Its properties have been altered to such a degree that it no longer has a tendency to felt during washing and consequently is non-shrinking also.

With reference to the preparation of the padding liquors for use in examples which follow, the procedure may consist of diluting the prepared polymer emulsions with water. When two emulsions are used, the emulsions are usually mixed in the proper proportions and then diluted with water to the proper concentration. The following table will illustrate this procedure for padding liquors used in Example 1.

Preparation of 300 parts of padding liquor containing 5% polymers.

ercent Composition 68.67 N w w Polymer Rho I a r 89m reno Later 0 p Nfilaine Rhplex ER p parts umrts 3513' 5 The other examples were prepared in a' similar manner. when only one emulsion is used. the emulsion is simply diluted with water to a 5% concentration.

The following examples illustrate the inven- -tion, the parts being by weight unless otherwise indicated.

Example 1.-A series of three padding solutions was prepared using polychloroprene and polyethyl acrylate' emulsions. known to the trade as "Neoprene latex type 571i and Rhoplex ER respectively. Samples of wool flannel 10" x 10" in size were padded from these solutionsand the excess of pad liquor was removed by passing the sample through squeeze rollers. The weight of the wool samples was noted before and after padding and.

from the weight increase the amount of polymer applied to the fabric was calculated. The composition of the polymer and the amount deposited on the fabric are shown in Table I.

The samples were dried at approximately 80 C.

and four lengths of 8" each were marked on each sample, two in the direction of the warp and two in the direction of the fill.

The wool samples were then washed for 3 hours in a mechanical washing machine.

The samples were rinsed and dried and the measurements were taken again. The percentage shrinkage in warp and fill direction is shown in Table IV.

Table I Per cent pof Polymer Polymer De ited mm Polychloroprone Polyethylacrylate ems I washed in a solution of 2% neutral soap in hot water (70 0.). After rinsing and drying the samples were measured and the warp and flll shrinkage were calculated. The felting as well as the shrinkage in per cent may be found in Table Table II 1, 7 Per cent Comp. of Polymer Sample No. Y

posited Pol chloro- Vegetable Oil on wool gl'efle Factlca Example 3.A series of four padding liquors x 6 was prepared from polymethyl methacrylate and polychloroprene emulsion known to the trade as "Methacrol Bl?" and "Neoprene latex type 5'71" respectively.

These emulsions were mixed and diluted with water in such a way that the padding bath contained 5% solids. Squares of wool flannel (10" x 10") were immersed in these solutions, until they were completely wetted out. and then the excess or liquor was removed by passing the fabric through squeeze rollers. The amount of liquid absorbed by the fabric was noted and the quantity of solids deposited on the wool was calculated. The amount of polymer so deposited and the polymer composition may be found in Table III.

A square of the same wool flannel was immersed in water at room temperature until it was thoroughly wetted out. The excess water was removed by passing through the squeeze rollers.

The treated samples as well as the untreated square were then dried at approximately 60 C.

The five samples were measured. washed, rinsed and dried as explained in Example 1.

After drying the samples were measured again and the percentage shrinkage in the warp and in the fill as well as the degree of felting may be found in Table IV.

Table III Per cent Per cent Comp. of Polymer Sample No.

g?$ g Polychloro- Polymethylprene methacrylate 7 6. 13 15 8. 5. 91 75 25 5. 92 60 40 10 6. 26 0 l1 (untreated).

Table I V Per cent Shrinkage after 3 hr. washing Sample No. Felting Warp Fill 1.. 5. 3 3. 1 None. 1 42.- a a 1. 2 Slight.

3. 12. l 2. 8 Moderate. 4.- 21. 6 3. 3 Do. 2 5.. 28. l 5 2 Considerable.

6.. 32. U 5. 2 Do. 7.- l7. 8 5. 3 Moderate. 8.- 20. 5 4. 6 Do. 3 9.- 20. 0 3. 6 Considerable.

l0. 3. 7 1. 6 None. 11 39. 9 19. 3 Very bad.

Example 4.A treating bath was made by mixing 280 parts water. 1.19 parts of a straight polychloroprene emulsion containing 58.6% solids, as mentioned in Example 2, .06 part of sodium lauryl sulfate and 1.4 parts of acetic acid 50%. The bath was heated to 65 C. and a swatch of wool weighing 13.9 parts was immersed in this bath. The wool was agitated for 10 minutes and then 7 parts of 15% solution of anhydrous sodium. sulfate was added. The fabric was agitated continuously, and further additions of sodium sulfate solution were made at 5 minute intervals. After a total of six such additions had been made, the bath exhausted completely. The wool was then rinsed and dried at 60 C. and four lengths of 8" each were marked on the sample, two in the direction of the warp and two in the direction of the fill. The sample was then washed for 3 hours with soap and water in a mechanical washing machine. After the washing the sample was rinsed and dried, and measured again. The percentage of shrinkage in the warp and flll direction is listed in Table V.

Example 5.-14.0 parts of wool flannel was immersed in a bath consisting of 280 parts of water and 1.12 parts of glacial acetic acid. The temperature of the treating bath was kept at 65 C. during the entire operation. After 5 minutes 2.8 parts of a straight polybutadiene emulsion (25% solids) was added to the bath and the wool sample was agitated. The polybutadiene emulsion was prepared according to the procr dure described in Rust and Pfeifer application Serial No. 603,406, filed July 5, 1945. Five minutes later 1 part of anhydrous sodium sulfate dissolved in 6 parts of water was added. These additions were repeated at 5 minute intervals until a total of 6 parts of the salt was added. The bath became completely clear 5 minutes after the last salt addition was made. The fabric was rinsed and dried. The sample was marked off, washed, rinsed, dried and remeasured as explained in Example 4. The shrinkage and degree of felting due to the laundering may be found in Table V.

The treatment with glacial acetic acid as given in the above example is to regulate the pH and is a prelude to the dyeing-out method employed in such examples. Any acid can be used in a concentration equivalent to the acetic acid as in dicated. Other examples will be found below.

Example 6.A swatch of wool weighing 12.5 parts was soaked in a solution of 250 parts of water containing 1.6 parts of 50% acetic acid for 5 minutes. At the end of this period of a straight polybutadiene (25% solids) emulsion prepared as described in Example '5, and 4.25% of a straight chloroprene emulsion (known commercially as "neoprene latex type 571, conc. 58.6% solids) were added. Both percentages are based on the weight of the wool. Also .05 part of sodium lauryl sulfate was added at this time. After 5 minutes 7% of anhydrous sodium sulfate (based on the wool weight) dissolved in a sumcient quantity of water was added and these additions were repeated until the bath exhausted completely clear. In order to accomplish this it was found that 42% of sodium sulfate was needed. The temperature of the bath was kept at 65 C. during the entire operation, andthe sample was agitated continuously. The swatch was then rinsed and dried. The washing and measuring procedure is described in Example 4, while the shrinkage and felting results are tabulated in Table V.

Example 7.A treating bath was prepared by mixing 300 parts of water at 70 C., .75 part polybutadiene emulsion (25% solids), prepared as described in Example 5, .96 part polychloroprene emulsion (58.6% solids), as used in Example 2, 2.18 parts of 50% acetic acid and .09 part of sodium lauryl sulfate.

A swatch of wool was immersed in this bath for 10 minutes and then 42.5% (based on the weight of the wool) of anhydrous sodium sulfate dissolved in suflicient water was added over a period of 30 minutes. The bath was kept at 65- C. during the entire operation and the wool was agitated continuously. The bath exhausted completely.

After rinsing and drying the sample was washed and measured as before. Shrinkage percentages and felting are listed in Table V.

Example 8.--14.6 parts of wool flannel was treated with a solution of 1.7 parts acetic acid 50%, in 290 parts of hot water (70 C.) for 5 minutes. At the end of this time there was added to the bath 2.2 parts of a 25% polybutadiene emulsion, prepared as described in Example 5, .37 part of a 49.4% polychloroprene emulsion, as mentioned in Example 2, and .03 part of sodium lauryl sulfate. The fabric was agitated in this liquor for 5 minutes whereupon 7 parts of a 15% anhydrous. sodium sulfate solution was added. The bath was kept at 65 C. and five more additions of 7 parts 15% sodium sulfate solution were made at 5 minute intervals. Five minutes after the last salt addition had been made the bath cleared up completely. Also a swatch of untreated wool was given a relaxation treatment. This was accomplished by soaking the fabric in a 1% neutral soap solution at room temperature for 2 hours. Both pieces of wool were then rinsed, dried and measured. For washing the procedure of Example 4 was followed. After the laundering the samples were rinsed. dried and remeasured. The percentage of shrinkage and the degree of felting are listed in Table V.

Table V Per cent Shrinkage after 3 hr. washing Example No. Felting Warp Fill 3. 7 +1. 6 Slight. 2.1 2. 3 None. 4. 2 1. 3 Slight. 4. 2 0 Very slight 2. 3 1.2 None. 38. 8 18.5 Very bad.

Example 9.-A series of five padding solutions was prepared using polychloroprene emulsion (known to the trade as neoprene latex type 571"), natural rubber latex and mixtures of these two products. These materials were used in the form of 5% aqueous dispersions. The compositions of these dispersions will be found in Table VI.

Samples of wool flannel 10" x 10" in size were immersed in these solutions for a sufficient length of time to insure thorough impregnation. The swatches were then passed through squeeze rollers, thus removing the excess pad liquor.

The weight increase was noted and the amount of polymer deposited was calculated. This information may be found in Table VI. A square of the same wool flannel was immersed in a .2% aqueous solution of sodium lauryl sulfate at room temperature. until thoroughly wetted out. The excess water was removed by passing the sample through the squeeze rollers.

The treated as well as the untreated squares were dried at about 60 C., allowed to cool and four lengths of '8" each were marked on each sample, two in the direction of the warp and two in the direction of the fill.

The squares were then washed for 3 hours in a washin machine containing sufficient neutral soap to produce a running suds. After rinsing and drying, the pieces were measured again. The percentage shrinkage in warp and fill direction as well as the degree of felting is tabulated in Table VII.

auaooe Table VI Parts Parts Parts wool wool liquid polywag before after picked mer 1 pn r up depd.

Table VI! Table IX P r cent shrinkage alter Percent shrinkage after 3 hr. washing 3 hr. washing Sample No. Felting l p fl N0- Felting Warp Fill Warp Fill 6. 4 4. 6 None. 8.0 4. 0 None. 15. 3 5. 0 Slight. 7. B 4. 3 Slight. 23. 2 7. 5 Moderate. 10. 5 5.1 Do. 20.3 6.0 Considerable. 4 7.9 5. 1 None. 5 27.0 a. 5 Bad. t o untreated 44. 1 so. 3. Very bad. 6 (untreated) 30.0 6. 5 Very bad.

Example 10.-A series of three padding solutions containing 5% solids utilizing various types of polychloroprene dispersions, These dispersions are known commercially as neoprene latex. A bath having a solids contents of 5% was prepared from a polybutadiene dispersion.- This polybutadiene dispersion contained solids and was prepared according to the method described in Rust and Pfelfer application Serial No. 603,406. Squares of wool flannel were immersed in these treating baths until completely wet, and the excess liquor was removed by passing the fabric through squeeze rollers. The samples were then dried at 60 C. The composition of the diiferent liquors as well as the amount of solids deposited on the wool may be found in the following table,

After drying the wool swatches, as well as an untreated control, which had been relaxed according to the procedure given in the previous example, were measured, and washed for 3 hours in a mechanical washing machine, containing water at 70 C. and sunlcient neutral soap to produce a running suds.

After washing, the wool squares were rinsed, dried and measured.

The shrinkage percentages and the degree of felting are given in Table IX.

Example 11 .-The padding solution of Example 3 10 was now adjusted in such a way as to contain 2% of solids. Samples of wool flannel were treated with these solutions, dried, washed and measured according to the procedure of the previous example. An untreated control was included in the washing. The amount of liquor absorbed by the wool will be found in Table X, as well as the amount of solids deposited on the wool, which amount was obtained by calculation.

* Table X s 1 Par oat Pelt cent amp a q 0 or No. Treating "quot picked u epo s ited by woo on wool Neoprene latex type 572 27 solids. 124. 5 2. 49 Neoprene latex type 571 o solids. 122. 8 Z 46 Neoprene latex type 60 solids... 121. 8 2. 44 Polybutadiene emulsion 2% solids. 113. 3 2. 27

The shrinkage. and felting observed after 3 5 Example 12.--Butadiene, 45 parts, was placed in a glass pressure bottle cooled to -15 C. Five parts of freshly distilled chloroprene were added. Ten parts of 1% aqueous potassium persulfatec were added to 114 parts distilled water. "This aqueous phase was added to the monomers. A

50% solution consisting of six parts of cetyl dimethyl benzyl ammonium chloride dissolved in 6 parts isopropanol was then added to the bottle. The bottle was sealed and placed in a shaking machine in a 12-15 C. water bath and shaken for 16 hours. The emulsion was then heated to 64 C. for 7 hours, then at 53-55 C. for 18 hours. A viscous homogeneous translucent emulsion was obtained. The emulsion contained 29% solids. A padding bath was prepared by diluting some of the emulsion with water until the solids content was A sample of wool flannel x 10" in size was padded from the solution and the excess padding liquor was removed by passing the wool through squeeze rolls. The calculated solids pick-up are listed along with the polymer composition in Table XII. The flannel was dried at approximately 60 0., measured as explained in Example 1. After rinsing and drying, the flannel was measured and warp and fill shrinkage were calculated. The i'elting as well as the shrinkage in percentage may be found in Table IHII.

Example 13.--Butadiene, 40 parts, and chloroprene, 10 parts, were subjected to emulsion polymerization in exactly the same manner as was used with the 45 butadiene and 5 chloroprene proportion of Example 12. Polymerization conditions of time and temperature were identical as were the water phase, catalyst and emulsifier. This emulsion also contained 29% solids on polymerization. v

A padding solution was prepared by diluting the above emulsion with water to adjust the solids content to 5%. W001 flannel was treated with this padding liquor, dried, washed, and measured according to the procedure of Example 12. The calculated solids picked up by the wool and the polymer composition will be found in Table XII. The amount of shrinkage in percentage and felt ng after laundering will be found in Table XIII.

Exam le 14.-Butadiene, parts. and chloroprene, 25 parts. were placed in a glass pressure bottle cooled to below 15 C. Ten parts of 1% potassium persulfate were dissolved in 115 parts of water containing 6 parts cetyl dimethyl benzyl ammonium chloride and 6 parts isopropyl alcohol. This water phase was cooled to 5 C. and added slowly to the monomers. The pressure bottle was then sealed, placed in a shaking device in a 12-15 C. water bath and shaken for 6 hours. The bath temperature was then raised to 46v C. over a 4 hour period, then held at that temperature for 9 hours. The temperature was then raised to 53 C. for 3 hours. Polymerization was complete and a homogeneous emulsion was obtained. Solids content was 2'7 A portion of the emulsion was oxidized by refluxing with 5% of its weight of hydrogen peroxide solution for 1 hour. The oxidized emulsion was diluted to a 5% solids concentration by adding distilled water to form a padding liquor.

Wool flannel was treated with the above padding liquor, dried, washed, and measured ac cording to the procedure of Example 12. The calculated solids picked up by the wool and the polymer composition will be found in Table XII. The amount of shrinkage in percentage and felting after laundering will be found in Table XIII. A piece of untreated wool was relaxed by soaking in 1% soap solution for 2 hours, rinsed, dried, and measured as a control as seen in Table XIII.

Table x11 Per cent 332 Percent composition of polymer g g gggi (calm) 1 butadiene, 10% chloroprene (Ex- 6.0

amglel 2 80% utadlene, 20% chloroprene (Ex- 5.8

am e 3 50% butadiene, 50% chloroprene (151- 5.1

. ample 14).

Table XIII Percent shrinkage after 3 hr. washing Sample No. Felting Warp Fill 1 2.6 0.0 None. 2 2.4 0.3 Do. 3 6.0 3.6 Do. Control 22.6 4.0 Very bad.

Example 15.-Chloroprene, 22.5 parts, and styrene, 2.5 parts, were placed in a pressure bottle cooled to 10 to -15 C. A water phase consisting of 3 parts Ivory soap flakes, 3 parts isopropanol and 5 parts of 1% aqueous potassium persulfate, dissolved in 57.5 parts distilled water was added to the monomers. The bottle was sealed. shaken thoroughly, then placed in a shaking device in a water bath at 1015 C. for 16 hours. Heat was applied to the bath and the temperature reached 55 C. after 3 hours. Heating was continued for 6 hours. The pressure bottle was then cooled and the emulsion removed. Suificient ammonia was added to raise the pH of the emulsion to approximately pH 8. A portion of the emulsion was diluted with water until the solids content was approximately 5%, to form a padding liquor. A sample of wool flannel was padded in the emulsion, dried, washed and measured according to the procedure of Example 12. The polymer composition and the calculated solids picked up by the wool are listed in Table XIV. The amount of shrinkage in percentage and the amount of felting after laundering may be found in Table XV.

Example 16.-An emulsion was prepared exactly like that in Example 15, except that 2.5 parts of acrylonitrile were used instead of the 2.5 parts styrene used in Example 15. Polymerization and wool treatment were identical with Example 15. The polymer composition and the solids picked up by the wool are listed in Table XIV. The amount of shrinkage in percentage and the amount of feltingmay be found in Table XV.

Example 17.Chloroprene, 20 parts, and methyl methacrylate, 5 parts, were placed in a pressure bottle cooled to 10 to 15 C. Six parts of a 50% solution of cetyl dimethyl benzyl ammonium chloride in isopropanol were dissolved in 57.5 parts distilled water, 5 parts of a l aqueout solution of potassium persulfate were added and the water phase was cooled to 5 C. and added slowly to the above monomers. The pressure bottle was sealed and placed in a shaking device on a water bath and shaken for 16 hours at 10-15 C. Heat was applied for 3 hours until the temperature reached 55 C., then heating was continued for 6 hours at that temperature. The emulsion was cooled to room temperature, then diluted to 5% solids concentration. A sample of wool flannel was padded in the emulsion, dried,

. l3 washed, and measured according to the procedure explained in Example 12. The polymer composition and the calculated solids picked up by the wool are listed in Table XIV. The amount of shrinkage in percentage and the amount of felting after laundering are listed in Table XV.

Example 18.-An emulsion was prepared exact- 1 1y like that in Example 17 except that 5 parts of ethyl acrylate were used instead of the 5 parts of methyl methacrylate used in Example 17. Polymerization and wool treatment were identical with Example 17. The polymer composition and the solids picked up by the wool are listed in Table XIV. The amount of shrinkage in percentage and the amount of felting after laundering may be found in Table XV. A piece of untreated flannel was relaxed by soaking in a 1% soap solution for 2 hours, rinsed, dried, and measured as a control For the best shrinkprooflng effects, the emulsions contain the copolymer in a condition in which it is unsuitable as synthetic rubber or rubber-like material. If coagulated by any suitable means, the emulsions give crumbly materials which cannot be milled or sheeted as on rubber milling equipment in the way that rubber is manipulated. The copolymer is in the form where extensive cross-linking has occurred as further T pointed out below.

To enhance such materials for use for shrinkproofins. they may desirably be given an oxidation treatment, preferably while in aqueous emulsion as obtained from the polymerization step. to convert them into what may be called a pro-vulcanized condition so that upon deposition of the polymer on, in or about the fibers or textiles, the polymer is in anon-tacky condition and gives a nontacky deposit. Or the polymer in such emulsions utilized in accordance with the present invention employed, the emulsions are prepared by 'carrya ing out the polymerization in the presence of polymerizing agent in which emulsions the polymer completely vulcanized, and the emulsion thus prepared is subjected to an oxidative treatment by means of hydrogen peroxide or other substances which liberate oxygen under the conditions of treatment to convert the polymer or copolymer present in such emulsions. into a condition where upon deposition on fibers it gives a non-tacky deposit, or gives a deposit which is substantially insoluble in common organic solvents, or is substantially completely vulcanized and in the form of a cross-linked polymer. The first step is carried to a point of substantially complete polymerization, by which is meant little or no monomer is present. The emulsion at this point may be subjected to vacuum or other treatment to remove any volatile hydrocarbons which may be present, before the step of oxidative vulcanization. The term oxidative pre-vulcanization may be used to describe the flnal condition of the polymer in the emulsion without any implication that an oxygen link is necessarily involved.

Such oxidative pre-vulcanization may be carried out at temperatures for example of 10-100" 6., with oxygen yielding substances such as hydrogen peroxide, benzoyl peroxide, ammonium persuli'ate, acetyl peroxide, butyl hydroperoxide, butyl perbenzoate, etc., for a period of from 45 minutes to 1% hours. Such oxidative treatment ofthe emulsion is desirably carried out in the absence of the antioxidants, the latter being added after the oxidation treatment has been carried to the point desired. This addition of antioxidant is desirable so that further oxidative change will not continue after the material has been applied to the textile.

Surprisingly, it has been found that an antioxidant has a very direct and important effect in V enhancing shrinkproofing and other desirable qualities in the treated wool. These antioxidants may vary in character but generally are the phenols and amines particularly of aromatic character such as monobenzyl ether of hydroquinone, phenyl p-naphthylamine, p-hydroxyphenyl glycine, etc. The amount present should be suflicient to secure the result desired, small amounts as from 1% to 5% on the weight of the polymer usually being sumcient not only to improve shrinkprooflng extensively but to give the treated product increased heat resistance, etc. For instance wtih a 3% application of a soap emulsion of butadiene polymer containing 1%% of monobenzyl ether of hydroquinone, a 5% shrinkage in the warp was found after 10 washings at F. for 10 minutes. In a similar fabric containing the same amount of butadiene polymer but containing no monobenzyl ether of hydroquinone, a 17% shrinkage in the warp was found. The eflect of th antioxidant on shrinkproofing results obtained is therefore, important and noteworthy.

.This application is a division of application 15 amount to give from 1 to 25% by weight on the wool, the emulsion containing a non-cationic emulsifying agent and at least 25% by weight on the copolymer present or a water-soluble neutral salt of an alkali metal as a conditioning electrolyte, the pH of the bath being below '7.

2. A bath as set forth in claim 1, in which the methacrylate is methyl methacrylate in amount not exceeding 20%.

3. A both as set forth in claim 1, in which the methacrylate is ethyl methacrylate.

4. A bath as set forth in claim 1, in which the methacrylate is butyi methacrylate in amount not exceeding 40 5 antioxidant tor the copolymer.

JOHN B. RUST.

REFERENCES CITED The following references are of record in the 10 file of this patent:

UNITED STATES PATENTS Name Date Young Feb. 1, 1944 Number 

